EP0628642A1

EP0628642A1 - Superhard film-coated material and method of producing the same

Info

Publication number: EP0628642A1
Application number: EP94902089A
Authority: EP
Inventors: Yasushi Osaka Diamond Industrial Co Ltd Matsumoto; Kazuhito Nishimura; Hiroshi Osaka Diamond Industrial Co Ltd Tomimori; Akio Osaka Diamond Industrial Co. Ltd. Hara
Original assignee: Osaka Diamond Industrial Co Ltd
Current assignee: Osaka Diamond Industrial Co Ltd
Priority date: 1992-12-08
Filing date: 1993-12-08
Publication date: 1994-12-14
Anticipated expiration: 2013-12-08
Also published as: KR940703936A; WO1994013852A1; DE69330052D1; KR100193546B1; US5955212A; EP0628642B1; EP0628642A4; DE69330052T2

Abstract

This invention provides a superhard film-coated material consisting of a superhard film of diamond or the like, and a superhard alloy base material to which the film is fixed firmly; and a method of producing the same. According to the present invention, a superhard alloy base material is heat treated so as to deposit hemispherically on the surface of the base material a combined metal in the portion of the base material which is close to the surface therhof. This invention is characterized in that diamond and/or diamond-like carbon is formed by a chemical vapor phase synthesis on the surface of the base material by leaving the deposited metal as it is or removing the deposited metal partially or wholly. Owing to the formation of this deposited metal, the combining force of the superhard film and superhard alloy base material increases remarkably, and the formation of a thick film becomes possible.

Description

Technical Field

The present invention relates to a superhard film-coated member for use in cutting or wear resistant tools, wear resistant parts and components, optical parts and components, electronics materials and the like, which is produced by forming a film of diamond and/or diamond-like carbon on the surface of a cemented carbide substrate in a chemical vapor deposition process. The term "superhard film" herein referred to shall generically means films formed of diamond and/or diamond-like carbon.

Background Arts

Chemical vapor deposition, in providing diamond coating on the surface of a cemented carbide substrate, tends to produce amorphous carbon on the cobalt in the bonding phase (hereinafter also referred to as bonding cobalt, and such bonding cobalt and like metals in the bonding phase as bonding metals), which hinders formation of diamond. As one solution to this problem, the prior art, typically exemplified by Japanese Patent Publication No. Sho 63-20911, discloses that acid etching the substrate to remove the bonding metal to a predetermined depth from its surface has the effect of allowing formation of the diamond film thereon and remarkably improving the bonding strength between the diamond film and the substrate.
Further, Japanese Patent Publication Laid-Open No. Sho 63-100182 discloses that a cemented carbide of which the content of bonding cobalt is reduced by about 1 to 4 % by weight is suitably used as a substrate for diamond coating, but that for diamond film formation such a low-cobalt cemented carbide still requires acid etching to have its bonding cobalt removed.
Alternatively, Japanese Patent Publication Laid-Open No. Sho 62-67174 discloses several methods of bonding metal removal, including dry etching the substrate in a plasma of carbon fluoride, sputter etching with hydrogen, argon gas, etc., besides the aforementioned method using an acid.
In the meantime, there has been proposed a formation of an intermediate layer to improve the bonding strength between the diamond film and the substrate without removing the bonding phase as above. For example, Japanese Patent Publication Laid-Open No. Sho 63-1280 discloses forming on the surface of a cemented carbide or a like substrate a layer of a carbide, nitride, boride, etc. of an element of Group IVa, Va or VIa of the periodic table, or a compound or a mixture of these, and then providing a diamond film on the thus formed layer.
Also, as to the thickness of the superhard film coating, Japanese Patent Publication Laid-Open No. Hei 1-212491 describes that a thickness exceeding 20 micrometers is not desirable because such thicker film coating will delaminate due to thermal stresses occurring in the coating.
As described hereinabove, many proposals have been made so far for the improvement of the bonding strength of the diamond film to the substrate, but no appropriate methods assuring satisfiable quality and adapted for industrial production have been found yet, thus leaving the development of such appropriate methods highly required still.
In other words, since a cemented carbide subjected to acid etching has the bonding metal thereof removed from its surface layer, WC (tungsten carbide) particles existing in the interface between the substrate and the diamond film are not always firmly retained at their fixed positions (in a case using WC as the substrate). A diamond film formed on such interface cannot have a sufficient bonding strength, and thus the resultant cutting tools are limited in their usage only to cutting of low (below 12 %) silicon-aluminium alloys, graphite, carbon fiber-reinforced plastics, green ceramics , etc., being incapacitated for interrupted cutting of 18-20%Si-Al alloys or heavy-dutycutting such as high feed cutting and deep cutting over a prolonged period of time.
In addition, if a diamond film grows to a thickness close to 15 micrometers on an acid etched cemented carbide, it will delaminate of itself. Thus, so long as the coating on the surface of cemented carbide is concerned, the prior art process allows only a diamond film having a thickness in the range of about 0.1 to 5 micrometers in the respect of the prevention of such delamination , and consequently the resultant tools will have their substrates exposed before their flank wears (Vb), used as a measure of tool life, reach a predetermined amount, even if delamination of the diamond film could be avoided.
Thus, the resultant tools will inevitably have a limited useful life.
Accordingly, the present invention solves the foregoing problems of the prior art by providing an improved cemented carbide coated with a superhard film having a high bonding strength, the film being allowed to grow thicker to produce a superhard film-coated cemented carbide with a longer life, and by providing an improved and novel method for producing such a diamond-coated cemented carbide.

Disclosure of the Invention

The inventors have undertook a series of study works with a view to permitting a cemented carbide substrate to be coated with a superhard film by heat-treating the substrate without using a preceding acid etching process to remove the bonding metal from the substrate, and permitting to provide such a coating of greater thickness having a high bonding strength by making the coefficient of thermal expansion at the surface of the substrate closer to that of diamond, to find the followings.

1) Heat-treating the cemented carbide substrate singly or repeatedly will produce on the surface of the substrate hemispherical deposits mainly composed of the bonding metal.
2) If the substrate is pretreated by repeating the foregoing heat treatment at least one time, followed by formation of the superhard film on its surface, the resultant coated cemented carbide can have a superhard film thicker than 20 micrometers with a high bonding strength.
3) Heat-treating the substrate in an atmosphere containing carbon atoms will produce on its surface hemispherical deposits together with sediments mainly composed of carbon. Repeating the heat treatment and the removal of the 8 sediments at least once is effective in forming on the substrate a thick superhard film having a high bonding strength.
4) The cemented carbide substrate after being passed through the heat treatment as described in the foregoing paragraphs 1) and 2) will have such a region within the depth of about 30 micrometers from the surface in which the bonding phase content is reduced and the hard phase interparticle spaces become narrower than those in non-treated substrates, so that the substrate can retain at least its original strength which is sufficient for the manufacture of tools to be used in interrupted cutting or heavy-duty cutting such as high feed cutting and deep depth cutting. Also, the thus treated substrate will exhibit at its surface a smaller coefficient of thermal expansion close to that of diamond
5) In the resultant superhard film-coated cemented carbide, the structure of the aforementioned surface of the heat-treated substrate and the existence of the deposits at the interface of the superhard film and such a substrate effectively improve the bonding strength therebetween.

The present invention set forth hereinbefore in the form of conceptual means to solve the prior art problems as well as the preferred examples (best mode for carrying out the invention) to be described hereinbelow are all given in the form using as the base material or substrate commercially available general purpose cemented carbide typically represented by WC-Co based alloys, although as a matter of course the present invention is practicable by using as the substrate other cemented carbides such as those containing free carbon, those as sintered, or those containing a bonding metal other than cobalt. Also, in the practicable processes shown in the preferred examples, there may be added any known or new processes, such as scratching the substrate surface prior to the film formation process (5) to be described hereinafter. Especially, for those cemented carbides having surface roughness of 0.2 µmRa or less, it is essential to apply the scratching process prior to heat treatment.

Brief Description of the Drawings

FIG. 1 is a schematic cross-sectional view of a hot filament CVD reactor used for the heat treatment and the film formation in a preferred method according to the present invention;
FIG. 2 is a photograph of a secondary electron image of scanning electron microscope, showing a particulate structure on the surface of a cemented carbide substrate used in the present invention;
FIG. 3 is a schematic representation illustrating the structure shown in FIG. 2;
FIG. 4 is a microstructural photograph showing an initial stage of diamond deposition on the substrate surface shown in FIG. 2;
FIG. 5 is a microstructural photograph showing a state in which the diamond is further grown from the state of FIG. 4;
FIGs. 6a, b and c are microstructural photographs, respectively, showing a structural composition of an interface between substrate and diamond film;
FIG. 7 is a photograph of a secondary electron image of scanning electron microscope, comparatively showing in section two particulate structures on the surfaces of cemented carbide substrate;
FIG. 8 is a graph plotting the quantity of deposits against the temperature of the substrate under heat treatment;
FIG. 9 is a graph plotting the quantity and size of deposits against the heat treatment time;
FIG. 10 is a photograph of a reflecting electron image of scanning electron microscope, showing the surface of heat-treated cemented carbide substrate;
FIGs. 11a, b and c are analytically enlarged views of FIG. 10, respectively;
FIG. 12 and 13 are photographs of secondary electron images of scanning electron microscope after cutting test, showing the cutting edges of a commercially available cutting tool and the present invention, respectively;
FIG. 14, 15, 16 and 17 are graphical charts showing the results of cutting tests made by using cutting tools of comparative examples and those embody ing the present invention;
FIG. 18 is a chart showing the thicknesses of superhard films achievable with the methods of comparative examples and the present invention, respectively.

Best Mode for Carrying out the Invention

Two groups of cemented carbide substrates as specimens were subjected to the following preferred series of processes. The first group comprised commercially available cemented carbide tips of WC-4%Co, while the second group comprised commercially available cemented carbide tips of WC-25%Co.
1. Heat treatment → 2. Soot removal → 3. Heat treatment → 4. Soot removal → 5. Film formation → 6. Grinding and polishing
Each process will be described hereinlater, with the major process conditions given below:

Heat treatment (1, 3)

Equipment used set A - hot filament CVD reactor shown in FIG. 1
set B - gas carburizing furnace

	set A	set B
Gas composition	H₂-1%CH₄	H₂-3%C₃H₈
Gas Pressure
	100 Torr	1 atm
Substrate temperature
	900 °C	900 °C
Keeping time (min.)	1, 3, 5, 15, 30, 45, 90, 180, 270 (common to A and B)

Soot removal (2, 4) Soot (sediments) produced on the substrate surface was wiped off with a swab (common to all substrates).
Film formation (3) (common to all substrates)

Equipment used	hot filament CVD reactor shown in FIG. 1
Gas composition	H₂-1%CH₄
Gas Pressure
	100 Torr
Substrate temperature
	900 °C
deposition time
	15 hours

Grinding (6) (common to all specimens)
ground with a #800 (30 µm) resin-bonded diamond grinding wheel

Process Details

Heat treatment (1, 3)

For heat treatment processes 1 and 3, a CVD reactor was used as shown in FIG. 1 comprising a reaction vessel 1, an inlet valve 2 for introducing an atmosphere gas into the vessel 1, a tungsten filament 3, a substrate cooling holder 4, a cemented carbide substrate as a specimen to be treated, and an outlet valve for discharging the atmosphere gas from the vessel 1.
The tungsten filament was connected to 120 V AC source to be heated with 120 ampere current to a temperature ranging from about 2,150 to 2,200 °C.
In the reactor, the substrate was spaced apart about 10 mm from the hot filament and maintainted at 900 °C as shown above.
In FIG. 2 is given a photograph of a secondary electron image of scanning electron microscope, showing partly in section a particulate structure in the surface region of a heat-treated sample of cemented carbide substrates belonging to the first group and set A, with a corresponding schematic illustration shown in FIG. 3.
As shown in FIGs. 2 and 3, the heat treatment caused bonding cobalt 11 to migrate out from the inside to deposit on the surface of the substrate, so that the bonding cobalt became hemispherically protuberant deposits 12 without spreading over the entire surface of the substrate. Conversely, inside the substrate there remained regions 13 having their bonding metal content reduced due to such deposition.
Such regions with reduced bonding metal content were observed within about 30 micrometers deep from the surface of the substrate. In those regions, the hard phase particles 15 of WC were rearranged, resulting in the paticles being more closely spaced from one another than in deeper regions of the substrate.

As summarized in the following table, formation of deposits 12 and diamond film was observed on the surfaces of some specimens, with those of set A heat-treated in the CVD reactor for 10 minutes or longer all showing such formation of deposites for both the first and second groups. In FIG. 3, reference numeral 14 denotes soot sedimented on the substrate surface and 16 is diamond formed through the aforementioned series of processes.

Formation of deposits through heat treatments and deposition of diamond films 10 µm thick
Heat treatment time (min.)	0	5	10	15	30	45	90	180	270
Deposits formation
First group
Set A	N	N	Y	Y	Y	Y	Y	Y	Y
Set B	N	N	-	N	-	N	-	Y	Y

Second group
Set A	N	N	Y	Y	Y	Y	Y	Y	Y
Set B	N	N	-	N	-	N	-	Y	Y
Set c	-	N	-	N	-	N	-	-	-

Film formation
First group
Set A	N	Y	Y	Y	Y	Y	Y	Y	Y
Set B	N	N	-	N	-	N	-	Y	Y

Second group
Set A	N for all specimens
Set B	N for all specimens
Note: In the table, the symbol N denotes "none" and Y denotes "present" for deposits formation, while for film formation N denotes "impossible" and Y "possible", with the simbol "-" standing for "non tested" for both items.

Soot removal (2, 4)

Sedimented soot was entirely removed from the surface of heat-treated specimens. In removing the soot, deposits 12 were left unremoved almost as they were on the surface.
The deposits were mainly composed of cobalt as a bonding metal, with slight amounts of tungsten and carbon, etc. It is desirable to remove soot or the like substances sedimented on the deposits comprising the bonding metal separated out from inside of the substrate, because such sediments hamper the growth of deposits. For the set A of specimens, two 90 minutes heat treatment processes combined with two soot removal processes were sufficient to assure formation of the deposits. The temperature of heat treatment may be selected suitably in the range of 500 to 1,300 °C in an appropriate balance with the retention time in the heat treatment equipment used. However, desirable results would be achieved with a temperature higher than that used for the succeeding film formation process.

Film formation (5)

As understood from FIG. 4, formation of nucleation of diamond particles initially began on the peripheries of the bonding metal deposits and at portions on the substrate surface free of such deposits. Subsequently, a diamond film grows to enclose the deposits so as to cover the substrate surface.
Photographs of FIGs. 6a, b and c show cross sections of interfaces between substrate and diamond film at the same location, with Fig. 6a showing a secondary electron image of scanning electron microscope, Fig. 6b an X-ray image of cobalt Kαl, and Fig. 6c an X-ray image of tungsten Lαl.
These X-ray images were taken by using the same LiF receptor. In the secondary electron image of FIG. 6a, the boundary between the substrate and the diamond film is identifiably observable. It is seen that the tungsten is definitely demarcated from the diamond, while the cobalt exists in the diamond side of the boundary. The cobalt found on the diamond side seems the trace of the aforementioned deposits. In the thickness of diamond films, the cobalt could be found within several micrometers from the surfaces of the respective substrates, namely, in a range approximately half the thickness of diamond films in the inventors' opinion.

Grinding or polishing (6)

The surface roughness of diamond-coated cemented carbide specimens was about 2 µmRa, which could be finished to 5 nmRa by grinding. Further, according to the present invention, it is possible to form even 30 µm or thicker diamond films on the substrate surfaces without delamination therefrom, and the resultant diamond-coated cemented carbide can be subjected to grinding. In the prior art, however, it has been impossible to form such diamond or diamond-like carbon films having a good adhesion strength to substrates, to say nothing of grind ability of cemented carbides coated with 20 µm or thicker superhard films.
In addition to the foregoing first and second groups of substrates, a third group of substrates were prepared to be subjected to a preferred series of processes, given below, for obtaining specimens of superhard film-coated cemented carbide, which resulted in formation of superior film coatings, as described hereinafter.
As the third group of substrates, were used commercially available cemented carbide 1/2 " square of WC-6% Co.
0. Pretreatment → 1. heat treatment → 2. soot removal → 3. heat treatments→ 4. soot removal → 5. film formation → 6. grinding or polishing → 7. cutting test

Process Conditions

Pretreatment of substrates (0)

Scratching	#80 SiC,sand blasting
Degreasing	supersonic cleaning in acetone

Heat treatment (1, 3)

Equipment used	hot filament CVD reactor
Gas composition	H₂-0.6%CH₄ (The gas was introduced into chamber after evacuating air by means of a rotary pump.)
Gas pressure	100 Torr
Temperature	filament temperature	2,180 °C
	substrate temperature	950 °C
Heat treatment time	90 min. X 3

Soot removal (2, 4) Soot (sediments) produced on the substrate surface was wiped off with a swab .

Film formation (5)

Equipment used	hot filament CVD system
Gas composition	H₂-1%CH₄
Gas pressure
	100 Torr
Temperature	filament temperature	2,180 °C
	substrate temperature	850 °C
Diamond deposition time	15 hours

Grinding (6) ground with a #800 (30 µm) resin-bonded diamond grinding wheel

Cutting test (7)

Machine used	Lathe manufactured by Mori Seiki Co., Ltd., Japan
Work material	Al-18%Si

Cutting conditions
	cutting speed	800 m/min.
	depth of cut	0.5 mm
	feed rate	0.1 mm/rev.
	wet,continuous cutting

Process Details

Heat treatment (1, 3)

FIG. 7 shows a secondary electron image of scanning electron microscope taken to observe, in vertically opposed position to each other, two cross section of the same heat-treated substrate of which one has deposits of bonding metal and the other is free of the deposits.
In the upper cross section (free of deposits), no pores are observable, because the interspaces between WC particles were filled with bonding metals even after heat treatment.
In the lower cross section (showing white upward protuberances), migration (deposition) of the bonding metals to the substrate surface occurred together with rearrangement of WC particles, so that the bonding metals had their thicknesses reduced. Also, there were observed adjacent the deposits small pores which could not be filled during the rearrangement of WC particles. Namely,within at least about 30 µm deep in the surface regions of the substrates, the bonding metal content was reduced and hard crystalline particles 15 of WC were more closely spaced from one another than in deeper regions of the substrate, supposedly bringing the coefficient of thermal expansion of the WC substrate nearer to that of diamond so as to bring about a continuous gradient of such coefficient between the substrate and the coating.
Further, as shown in FIG. 4, nuclei of diamond crystals were not formed on the deposits, but diamond-like carbon was supposedly formed thereon, so that the film coating would not bonded to the substrate there so strongly. This would contribute to relieving thermal stresses acting on the diamond films and the substrate.
In the graph of FIG. 8 is shown the number of deposits formed on the surface of substrates heat-treated at varied substrate temperatures in hot filament CVD reactor under the following conditions: filament temperature 2,200 °C; gas composition H₂-1%CH₄ (gas flow rate: H₂ 500 cc/min., CH₄ 5 cc/min.); distance between hot filament and substrate 10 mm; treatment time 1 hr. As seen in FIG. 8, the number of deposits increased remarkably at substrate temperatures ranging from about 900 °C to about 990 °C, with abrupt decrease at temperatures exceeding about 1,000 °C.
In FIG. 9 is also shown a graph plotting the number and the particle size of deposits against heat treatment time in experiments made by using hot filament CVD reactor under the following conditions: substrate cemented carbide of JIS K10 (WC-6%Co); gas composition H₂-CH₄ (gas flow rate: H₂ 500 cc/min., CH₄5cc/min., gas pressure 100 Torr); substrate temperature 950 °C; filament temperature 2,200 °C; distance between filament and substrate 10 mm.
As shown in the drawing, the number of formed deposits amounted to several tens per 50 µm square in 1 hour. As the heat treatment time became longer, the number of deposits became less, but their particle size increased.
FIG. 10 is a photograph of a reflecting electron image of scanning electron microscope, showing the surface of the heat-treated cemented carbide substrate treated at 950 °C shown in FIG. 8. In such a reflecting electron image, elements having larger atomic numbers are observed whiter, while those having smaller atomic numbers are observed darker. In the photograph of FIG. 10, blackpoints represent deposits, which are shown in an enlarged scale for analysis in FIG. 11a, b and c, with the deposits mainly composed of Co appearing darker, while the substrate surfaces composed of WC appearing whiter. FIG. 11a shows a secondary electron image of scanning electron microscope, Fig. 11b an X-ray image of cobalt Kαl , and Fig. 11c an X-ray image of tungsten Lαl.
For 1% methane concentration optimum heat treatment temperature ranges from about 900 °C to 1,000 °C, and 1 hour of treatment is sufficient to achieve formation of an acceptable quantity of deposits.
During heat treatment in the presence of methane gas flow, initialy amorphous carbon begins to sediment on bonding metals on the substrate surface, where deposits also begin to be formed. If the heat treatment is continued further, the deposits will be covered with amorphous carbon. Since this state inhibits the growth of deposits, a cycle of heat treatment and soot removal is repeated required times. As this cyclic process is repeated, the soot sedimentation decreases and diamond formation becomes remarkable on the substrate surface.
When heat treatment was conducted for 2 hours under the same conditions as given in FIG. 9 except that the atmosphere comprised only hydrogen gas with out methane gas flow, scanning electron microscopy revealed an extreme reduction in the formation of deposits.
This fact suggests that efficient formation of deposits requires supply of carbon atoms.
Based on the fact that when the deposits are covered with amorphous carbon the growth of deposits stops, but it is restarted if the soot is removed, it would be concluded that the deposits require for their growth exposition to excitons such as thermoelectrons emitted from the hot filament.
However, when the substrate was heated to 1,300 °C in an indirect heating type vacuum oven (5X10⁻³ Torr) with a smaller quantity of excitons, formation of deposits was observed.
This fact suggests that existence of excitons together with the presence of carbon atoms facilitates migration of bonding metals from the inside to the surface of the substrate. In the course of such migration, the substrate surface and the deposits would be polluted with the carbonaceous atmosphere and residual gases in the atmosphere, which supposedly causes the migrated bonding metals to grow into hemispherical deposits.
When the substrate was subjected to heat treatment under 100 Torr conditions relatively susceptible to plasma generation in which the substrate was exposed to thermoelectrons, deposits formation was observed at about 900 °C., but the temperature at which the deposits are formed would become higher if a heating oven with a smaller quantity of excitons was used. Therefore, to assure efficient formation of deposits, it is preferred to use as a heat treatment equipment a hot filament CVD reactor, although high-energy heating and other heating systems may be used, including microwave, laser beam heating systems, and the like.

Cutting test (7)

FIG. 12 is a photograph of a secondary electron image of scanning electron microscope, showing a diamond-coated cutting edge of a commercially available cutting tool after cutting a work of aluminium alloy (Al-18%Si) over a length of about 500 m. As seen in the photograph, the film coating was delaminated after cutting of this 500 m length of the work. The coating thickness is as small as about 10 µm or less, so that the grinding mark on the substrate surface can be observed on the diamond film.
FIG. 13 is a photograph of a secondary electron image of scanning electron microscope, showing a preferred tip of a cutting tool according to the present invention after cutting a work of the same material as above over a length of about 3,500 m, the tip being formed by repeating 3 times the 1.5 hour heat treatment under conditions shown in FIG. 9, followed by film formation in a H₂-1%CH₄ atmosphere over 15 hours with the substrate temperature kept at 850 °C. As seen in the photograph, no delamination occurred, with a slight wear observed on the flank. Also, the film coating thickness was significantly large, so that no grinding mark on the substrate surface could be observed.
FIG. 14 shows results of cutting tests made on the same cutting tool as that used in the experiment associated with FIG. 13 above, with the tip having its rake face and flank ground. In the tip, the film was grown to about 25 µm thickness, followed by grinding down to 15 µm thickness. In this test of which results are given in FIG. 14, were used as comparative examples the same commercially available cutting tool as that used in the experiment associated with FIG. 12 and a cutting tool with a tip formed of a substrate of the aforementioned third group without diamond film coating.
FIG. 15 shows in a graph form the drilling performance of the ground tip used in the foregoing test shown in FIG 14 above as compared with the performance of a non-ground tip formed of the same diamond-coated material as the ground tip, with the ground tip showing a remarkable reduction in its flank wear.
FIG. 16 is a graph showing the cutting performance of a preferred drill of the present invention formed of the diamond-coated member used in the test associated with FIG. 15 above, as compared with those of a drill formed of the cemented carbide material used for said diamond-coated member and of a commercially available diamond-coated drill.
FIG. 17 shows the cutting performance of a tool having the non-ground tip described with reference to FIG. 14 as compared with a tool having a tip formed of a material obtained by the heat treatment described with reference to FIG. 14 above, followed by removal deposits and formation of diamond film about 10 µm thick.
FIG. 18 shows a chart comparing maximum coating thicknesses achievable in the preferred examples, an intentionally prepared comparative example and a prior art comparative example.
In the specimens in which coating was provided without removing deposits, cobalt was found in the diamond film within a region on the side of the interface between the diamond film and the substrate, so that delamination of the film due to difference in the coefficient of thermal expansion between the film and the substrate was prevented more effectively, as described previously. Although such a desirable effect will not be achieved with superhard film-coated cemented carbides formed by removing deposits, such cemented carbides according to the present invention are far superior to commercially available products according to the prior art.
In experiments associated with the chart of FIG. 18, a commercially available diamond-coated tip has its coating thickness measured as one comparative example. As the other comparative example, a cemented carbide substrate as used for the present invention was immersed in a boric acid solution and subsequently subjected to film formation.
In the preferred example prepared without removing the deposits, diamond film is formed in the presence of the deposits, and the resultant inclusion of the deposits as trace in the diamond film would be effectively combined with the continuous gradient of such coefficient between the substrate and the coating due to reduced bonding metal content in the surface region of the cemented carbide substrate caused by migration of the bonding metals therefrom, so as to bring about a synergetic effect of allowing formation of thicker film with a high bonding strength.
In the preferred example prepared by removing the deposits, only the effect of migration to reduce the bonding metal content in the surface region of the substrate is observed, but such a preferred example is superior, in coating thickness and bonding strength, to both the prior art and boric acid-treated comparative examples.

Industrial Applicability

As described fully hereinbefore, the present invention provides a superhard film coated member by enabling formation, on a cemented carbide substrate, of thicker diamond films having a high bonding strength in a chemical vapor deposition process, which has been practically impossible according to the prior art, and the present superhard film-coated member has many applications including wear resistant cutting tools, wear resistant parts and components. Further, the present invention provides an aplicability to industrial production and an economical advantage, in that for the manufacture of the products the heat treatment and film formation processes are both performed by using the same CVD reactor.

Claims

A superhard film-coated member comprising a cemented carbide substrate and an superhard film of diamond and/or diamond-like carbon formed on said substrate, wherein said substrate has within about 30 µm deep from the surface thereof a region in which the hard phase interparticle spaces are narrower and the bonding metal phase content is lower than in the original substrate.
A superhard film-coated member according to claim 1, wherein said film contains therein the bonding metals of said cemented carbide substrate within a range of approximately half the film thickness from the interface at the surface of said substrate.
A superhard film-coated member according to claim 1 or 2, wherein the surface of said superhard film is ground.
A method of manufacturing a superhard film-coated member, comprising heat treating the surface of a cemented carbide substrate, forming hemispherical deposits mainly composed of bonding metals on said substrate surface, and then forming at least one substance to be selected from the group consisting of diamond and diamond-like carbon on said surface.
A method of manufacturing a superhard film-coated member according to claim 4, wherein said step of heat-treating said surface of the cemented carbide surface is performed in an atmosphere containing carbon atoms thereby to form on said surface hemispherical deposits mainly composed of bonding metal and sediments mainly composed of carbon, and further comprising removing said sediments formed on said surface or removing said sediments formed on said surface together with removal of all or a part of said deposits.
A method of manufacturing a superhard film-coated member according to claim 5, said steps of heat-treating said substrate and removing said sediments or removing said sediments together with said deposits are repeated at least twice.
A method of manufacturing a superhard film-coated member according to claim 4, wherein said step of heat-treating said surface of the cemented carbide surface is performed in an atmosphere containing hydrogen atoms or under low vacuum thereby to form on said surface hemispherical deposits mainly composed of bonding metal and sediments mainly composed of carbon.
A method of manufacturing a superhard film-coated member according to any of the preceding claims 4 through 7, wherein said cemented carbide substrate is heat-treated in a hot-filament CVD reactor.